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Preparation and properties of polyurethane / functionalized multi-walled

carbon nanotubes rigid foam nanocomposites

Article  in  Polimery -Warsaw- · November 2014

DOI: 10.14314/polimery.2014.776

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 Proceedings of the 5th International Conference on Nanostructures (ICNS5)
6-9 March 2014, Kish Island, Iran

Effect of 3- Aminopropyltriethoxysilane Functionalized Multi-Wall Carbon Nanotubes on

the properties of Polyurethane Rigid Foam Nanocomposites
Mir Mohammad Alavi Nikjea*, Alireza Yaghoubia
a
Department of Chemistry, Faculty of Science, IKIU, Qazvin, POBox: 288, Tel/Fax: +982813780040, Iran
*email: drmm.alavi@gmail.com

Abstract: Surface modification of the hydroxylated multi-walled carbon nanotubes (OH-MWCNTs) was carried out
by silanization with 3-aminopropyltriethoxysilane (APTS). Rigid polyurethane foam nanocompositeswere prepared by
silanized- MWCNTs in different weight percents via one shot method and thermal, mechanical and morphological
properties of the nanocomposites investigated in detail. The obtained results from thermogravimetric analysis indicated
that the thermal stability of nanocomposites was increased by increasing of silanized-MWCNTs content.
Morphological studies showed the increasing of cell density parallel by increasing of silanized-MWCNTs contents in
the polyurethane matrix. In the meantime, the results of tensile properties showed that the Young’s moduli as well as
tensile strengths were improved in comparison with pristine foam. Obtained data revealed reverse effects of 3%
functionalized MWCNT on the properties of respected nanocomposites due to agglomeration of MWCNTs.
Keywords: Multi-wall carbon nanotubes; Rigid polyurethane foams; nanocomposities; surface modification; 3-
Aminopropyltriethoxysilane

Introduction The OH-MWCNTs used in this work was purchased from

Currently, carbon nanotubes (CNTs) are one of the main
topics of research due to their extraordinary properties
such as high mechanical and thermal properties [1]. The
agglomeration of the CNTs and poor interaction between
the CNTs and matrix are two major problems that occur
during the preparation of CNT-reinforced composites.
Therefore, to overcome these problems, various methods
have been devised. Silanization of the CNTs by silane
coupling agents is one of these methods that can be used
to introducing of reactive functional groups as well as
improving of the surface properties.
This method was used by Velasco for the first time [2].
He modified the oxidized MWCNTs with 3-
mercaptopropyl trimethoxysilane (MPTS). It was shown
that silanization of CNTs with 3-mercaptopropyl
trimethoxysilane is an effective way that has lead to a
better distribution of the CNTs in the polymer matrix.
Rigid polyurethane foams are member of the family of
polymer foams that have a variety of applications in
everyday life which is due to their unique properties [3].
Pure PU due to its poor mechanical and thermal
properties is not suitable for many applications.
Therefore, Many researchers have attempted to solve this
problem [4]. In the present study, the OH-MWCNTs
were functionalized by silanization processes by using 3-
aminopropyltriethoxysilane (APTS) and the effect of
chemical functionalization of MWCNTs evaluated on the
mechanical, thermal and morphological properties of Si-
MWCNTs nanocomposites.
Materials and method
Materials
neutrino Co. (Tehran, Iran). The OH- MWCNTs had a
diameter range of 10–20 nm and 3.06 wt. % OH groups
according to the manufacturer’s data. DaltoFoam TAR
14066 polyether polyol containing all of required
additives and PMDI (SuprasecR 5005) for rigid PU foam
formulation were supplied by Huntsman Co. 3-
aminopropyltriethoxysilane (APTS), triethylamine
(TEA), ethanol, acetone were supplied from Merck.
Silanization of OH- MWCNTs with APTS and
Preparation of PUR foam nanocomposites
OH-MWCNT (1g) was dispersed in ethanol (250 ml) by
ultra probe for 5 min. Then distilled water (3 ml),
dispersed APTS (3 ml) in ethanol (50 ml), and TEA (1
ml), was dropped into the suspension sequentially. The
mixture was stirred at 900 rpm for 3 h. The final product
was then filtered, washed with ethanol and acetone and
dried in a vacuum desiccator at 80 ºC for 24 h.
For the preparation of nanocomposites; in first, different
amounts of silanized-MWNT, 1.5, 2 and 3 wt. %, were
added to the polyol matrix and sonicated in an
ultrasonicator for 10 min . Then the mixture was
transferred into a paper cup with a volume of 300 cc. In
the next step, PMDI was added to the polyol blend and
hand mixed. After foaming, the test samples were cured
at room temperature for 24 h. The weight ratio of polyol
to diisocyanate for all nanocomposites was 10 to 12.
Characterization
Fourier transform infrared spectrometer (FT-IR, Brucker
Tensor 27) was used to confirm the functionalization of
OH-MWCNTs. Thermal stability of the nanocomposites
was measured by a Thermogravimetry Analyzer (TGA,
 Proceedings of the 5th International Conference on Nanostructures (ICNS5)
6-9 March 2014, Kish Island, Iran

DuPont TGA951).The morphology of the samples, were

examined under a (S4160 Hitachi, Japan) Field Emission
Scanning Electron Microscope (FE-SEM). Tensile tests
were done using a Hegewald & Peschke measuring
instrument according to ASTM D412.

Results and Discussion

FT-IR Spectroscopy
The FT-IR spectra are shown in Fig. 1. In OH-MWCNT
spectrum, the bands at 3428, 1382 and 1056 cm-1, are
attributed to O-H stretching, bending in alcoholic groups Fig.2: SEM images of pure and Si-MWCNT-filled PUR foams:
(a) neat, (b) 1.5wt. % Si-MWCNTand (c) 3wt. % Si-MWCNT.
(C-OH) and C-O stretching, respectively. After the
silanization, the peak corresponding to C-OH bending
almost disappeared as well as was reduced the peak
intensity of O-H stretching, which are indications of
successful silanation. The peak at around 1052 - 1095
cm-1 related to Si-O stretching, but it is not clearly seen
due to overlap with other groups [2, 5, 6].

Fig. 3: SEM images of PURfoam nanocomposites: (a) 1.5 wt.%

Si-MWCNT, (b) is magnified image of (a), (c) 3 wt.% Si-
MWCNT And (d) is magnified image of (c).

Fig.1: FT-IR spectra of OH-MWCNT and Si-MWCNT
Analysis of morphology
The cell density for both nanophased and neat PUR are
shown in Table 1. Cell density ( ) is calculated using
the following equation [7]:
TGA analysis
Figure 4 shows the TGA curves for OH-MWCNT and Si-
MWCNT. The thermogram of the OH-MWCNT Shows a
weight loss of about 3% (in agreement with company)
which is attributed to the amount of OH groups on the
surface of the MWCNTs. After silanization of OH-
MWCNTs using APTS, The thermal degradation occur
between 40.9 and 383 ºC with a weight loss amount of
about 5.06% which is proportional to the amount of
coupling agent what coated the MWCNTs.
105
Weight Loss(%)

where n is the number of cells, A the area of the

micrograph in cm2, and M is the magnification factor. 95
SEM images of the samples are shown in Fig. 2 with a
magnification factor of 60. With increasing of MWCNT
particles, the cell density increased, and as a result, the 85 OH-MWCNT
cell size decreased. This increase is due to nucleation and
Si-MWCNT
growth phenomena during the foaming process. It can be
observed from figures 3b and d that the PUR containing 3 75
wt. % Si-MWCNT was severely agglomerated. However, 25 225 425 625 825
high surface energy between nanoparticles leads to Temperature(ºC)
agglomerate.
Fig.4: TGA thermograms of OH-MWCNT and Si-MWCNT
Table 1. cell density of PUR foam nanocomposites.
The thermal degradation of neat PUR and Si-MWCNT
Wt. % of Si-MWCNTs
0 1.5 3 nanocomposites has taken place in two stages which are
corresponded to the soft and hard segments, respectively
cell density )×10-4 [4]. The T50 for neat PUR matrix is observed around 447
1.10 4.45 4.90
ºC that was improved to approximately 464 and 463 ºC,
 Proceedings of the 5th International Conference on Nanostructures (ICNS5)
6-9 March 2014, Kish Island, Iran

at 1.5 and 2 wt. % Si–MWNT filled PUR
nanocomposites, respectively. This displays that the
thermal stability of the PUR foam nanocomposites is
improved by the addition of the Si-MWCNT to the
polymer matrix and interfacial interactions between
MWCNT and the PUR matrix [8].
Tensile characteristics
The typical stress–strain curves for the pure PUR and its
nanocomposites are shown in Fig.5. The modulus and
tensile strength of the 2 wt. % Si- MWNT
nanocomposites are enhanced by about 41.5% and 32.5%,
respectively as compared to the neat PUR. The
mechanical properties of the nanocomposites are shown
in Table 2. Enhancement of the mechanical properties of
the composites is attributed to the uniform distribution of
MWCNTs in the polyurethane matrix, and the strong
interfacial interaction between the MWCNTs and the
polyurethane matrix [9].
0.6
0.5
Stress(MPa)
increases with increase MWCNT content because
heterogeneous nucleation of MWCNT in PUR matrix. In
addition, the Young’s modulus of the PUR foam
nanocompositests increased by about 20.2 and 41.5%
with 1.5 and 2 wt. % silanized-MWCNT loading,
respectively resulted from tensile tests. Finally, compared
to neat PUR foam, thermogravimetric analysis revealed
that the degradation temperature (at a 50% weight loss) of
the PUR foam nanocomposites was increased by about
16.8 ºC and 15.5 ºC with the incorporation of 1.5 and 2
wt.% silanized- MWCNT loading , respectively.
Acknowledgments
The authors thank Imam Khomeini International
University (IKIU) for the financial supporting of Dr.
Alavi Nikje.
References
[1] S. Iijima, “Carbon nanotubes: past, present, and
future”, Physica B: Condensed Matter, 323 (2002)1-5.
[2] C. Velasco-Santos, A. L. Martinez-Hernandez, M.
Lozada-Cassou, A. Alvarez-Castillo, V. M. Castano,

“Chemical, functionalization of carbon nanotubes through

0.4 an organosilane”, nanotechnology, 13 (2002) 495-498.
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The OH-MWCNTs were functionalized via silanization [8] H. Xia, M. Song , “Preparation and characterisation of
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